N-beta-methylsulfonamidoethyl-p-phenylenediamines



Patented May 8, 1951 N -fl-1\IETHYLSULFONAMIDOETHYL-p- PHENYI-IENEDIAMINES Arnold Weissberger, Dudley B. Glass, and Paul W. Vittum,Rochester; N. Y., assignors to Eastman Kodak Company; Rochester, N. Y.,a corporation of :Newflersey No Drawing. Application March 18, 1949,Serial No. 82,281

7 Claims. (01. 260-556) This invention relates to photographic devel-.opers and more particularly to photographic developers of thesubstituted p-phenylenediamine type.

This application is a continuation-in-part of: our application SerialNo. 731,420, filed February 27, 1947, now U. S. Patent 2,548,574, whichis a continuation-in-part of application Serial No. 654,528, filed March14, 1946, now abandoned.

consisting of alkoxy groups and;substitutedalkoxW -roups; R1 representsa member selected% from the group consisting of hydrogen, alkyl groups,andwsubstituted alkyl groups; Rz represents an alkylene radical selectedfrom the group consisting of ethylene and propylene; andlita representsa member selected from the group consisting of alkyl groups andhydrogen.

Specific compounds which we contemplateus- It is known thatp-phenylenediamine photos 10 m include; graphic developers are valuablecompounds for 1 02m producing fine grain black-and-white photographicimages, and also, that these compounds, especially when they containalkyl substituents, (OHl),NHs02oH,- are useful as developers inprocesses for produc- 002E m colored photographic images. The Phen--1-amin0 3-ethoxy-N-ethyl N (18methylsulfonamideethyl). ylenediaminedevelopers, however, have several amlme defects. A common diflicultyencountered when 2 using these developers is their low activity and H2NN the low contrast and emulsion speed obtained 20 I \(CH)2NHSO CH3 withthem. Other disadvantages are their low 00H. solubility in developingsolutions and their aller- 4 in N meth 1 N (B methylsu1f namidoethy1).mgenie character, that is, their poisonousness to anisidine thehumanskin. I heselatter defects have. been 3, GZHE, solved,.. according.to v Weissberger U. S1 Patentl Y J 2,193,015, by adding. a.sulfonamidegroup. to one -Q of the nitrogen atoms. ofp-phenylenediamine. CHmNHSO'flHg Developers of this, type, however,exhibit low d velo i g activity. 4-'amino'-'N-ethy1 N (Bmethylsulfonamidoethyl) -m- A principalob'ject. of. the. presentinvention amsldme istherefbre, to. provide new developing agents 4 O3H7of the. substituted p-phenylenediamine type. hav- HQN ing highdeveloping activity and which are capable of giving high-contrastandemulsion speed. o0 H1 (OHMNHS 02cm We have discovered that thev rate ofdevelop- 4, 1N th 1 H ment with. sulfonamide substitutedp-phenyleneammo' {Jmpoxy g fi gy h fff l y Onaml diaminesis remarkablyincreasedby substituting, an alk'oxy group in. the, benzene ring, inortho 5? 02B: positionwith respect to the. primary amino group. These.novel compounds have the followinggen- 40 N: eral. formula: worn) zNHS'O5011 X R, 4-'amino=3-metl1oxy-5 methyl-N-ethyl N (B methylsulfonamidoethylyanilin'e- H21: N- 7 RiNH'SmRp 6 1411.

wherein X represents a member selected from the group consistingttofhydrogen, alkylgroups; (OHZMNHSONHB alkoxy groups, and substitutedalkoxy groups; Yrepresents a member selected from the group Thepreparation of these compounds is illuswas evaporated. The residue wasdistilled under t a by the p p o of 4-amino-3-eth0xyreduced pressurecollecting the portion that N ethyl-N-(p-methylsulfonamidoethyl)-aniline, boiled at 105-110/1 mm. as the desired product. which may besynthesized by the following The yield was 80 per cent. methods: 5 N-ethyl-m-phenetidine.0ne mole of N-ethyl- NO: NH:

2 51 r on 00,115 catalyst 00,11,

NHCzHs or alternately: (b) C O CH; VBIKCHI) :NHzJIB 1 N flL N 2 I sM M011.com l OH I OH hydrolyze CH CHgNHSOgCH; CH2CHINHSO2CH3 CHQOHZNH:

NCgH; NCzHs NCgH;

HONO CHaSO1C1 4- ocm, 00,115 7 00 B,

H: catalyst CHQGHNHSOQGH;

NCzH

The preparation of 4 amino N ethyl N- m-acetophenetide was boiled with150 ml. of

(6 methylsulfonamidoethyl) m phenetidine water and 150 ml. ofconcentrated hydrochlorid (Compound 1) may be illustrated by thefollowacid for six hours. The reaction mixture was ing procedure:cooled, made alkaline with 200 m1. of 40% N-ethyZ-m-acet0phenetide.-Amixture of one caustic solution and the amine was extracted mole ofm-phenetidine and one mole of ethyl with ether. The etheral solution wasdried over iodide was warmed in a waterbath to 40 at solid sodiumhydroxide and the ether was which temperature an exothermic reactionevaporated. The residue was distilled under rebegan. The temperature wasallowed to rise duced pressure collecting the portion that boiled to andthen was maintained at this temperaat, l48-150/l7 mm. as the desiredproduct. The ture for one hour first by coolin and as the yield amountedto per cent. exothermic reaction subsided by warming. After N (5mm'noethyl) N ethyl m phenotstanding overnight, the reaction mixture was60 idine.--A mixture of 1 mole of N-ethyl-mstirred with 200 ml. of waterand ml. of 40% phenetidine and 0.5 mole of fl-bromoethylamine causticuntil all of the solid had gone into soluhydrobromide was stirred andheated at tion. The amines were extracted with ether, for two andone-half hours. At the end the etheral solution was dried over solidsodium of this time the reaction mixture was cooled hydroxide and theether was evaporated. The 65 and 225 ml. of Water and 75 m1. of 40%caustic residue was added to 100 g. of-acetic anhydride solution wereadded. After all of the organic with stirring and cooling so that thetemperasalts had dissolved, the product was extracted ture did not riseabove 50. This mixture was with ether. The etheral solution was driedover heated on the steam bath for thirty minutes, solid sodium hydroxideand the ether was evapocooled and then stirred with 150 ml. of water 70rated. The residue was distilled under reduced until all of the excessanhydride had decompressure collecting the portion that boiled at posed.The mixture was made alkaline with at 148-150/l7 mm. as the desiredproduct. The 40% caustic solution and the product was exyield was 80 percent.

tracted with ether. The etheral solution was N (5 aminoethyl) N ethyl mphenotdried over solid sodium sulfate and the ether m-phenetidine.---Amixture of 0.625 mole of N (,6 aminoethyl) N ethyl m phenetidine and 250ml. of water was stirred vigorously, and 80 g. (0.7 mole) ofmethanesulfonyl chloride was added during a period of .30 minutes, thetemperature of the reaction mixture being kept at l5i5 during theaddition of the chloride. After each quarter of the acid chloride hadbeen admitted, one-fourth of a solution of 28 g. (0.7 mole) of sodiumhydroxide in 75 ml. of water was introduced. Ihe mixture was thenstirred for two hours at -25 and made alkaline with ammonium hydroxide.The amide was extracted with chloroform, the chloroform solution waswashed with water and dried over sodium sulfate. The chloroform wasevaporated under reduced pressure. The residue of crude amide amountedto 90 per cen N ethyl N ([3 methylsuljonamidoethyU- 4 nitroso mphenetidinQ.-.+One half mole of N g ethyl N (5 methylsulfonamidoethyD-m-phenetidine was dissolved in a mixture of 140 ml. of concentratedhydrochloric acid and 500 ml. of hot water. This solution was cooledquickly to 5 and maintained at this tempera? ture while a solution of 39g. (0.56 mole) of sodium nitrite in 50 ml. of water was added, withstirring, during a period of 20 minutes.

After standing at 5 for one hour, the reaction mixture was made alkalinewith ammonium hydroxide. The precipitate was filtered with suction andwashed with water. The moist product was recrystallized twice from 500m1. portions of 3-A alcohol and dried in air. The yield was 85 per cent.

4 amino N ethyl N (5 methylsulfonamidoethyl) m phenetidineoxalate-Onehalf mole of N ethyl N (B methylsulfonamidoethyl) 4 nitroso mphenetidine was dissolved in 500 ml. of absolute alcohol and reduced inthe presence of Raney Nickel at a a? hydrogen pressure of 45 lbs./in.and a temperature of 60. After the reduction was complete, the catalystwas filtered off and 0.5 mole of powdered, anhydrous oxalic acid wasadded. The mixture was warmed until all of the oxalic acid had dissolvedand then was cooled to 0 and allowed to stand until crystallization wascomplete. The crystals were filtered off, washed with absolute alcoholand dried in a vacuum desiccator over sulfuric acid. The yield was 80per cent.

4 amino N ethyl N ([3 methylsulfonamidoethyl) m anisidine (Compound 3),4 amino 3,5 diethoxy N ethyl N ({3- methylsulfonamidoethyl) aniline(Compound 6) and 4 amino 3 methoxy 5 methyl- N ethyl N (Bmethylsulfonamidoethyl)- aniline, 3,5 diethoxyaniline and 3 methoxy-5-methylaniline respectively.

4-amino -N-methyl-N (.B methylsulfonamidoethyl) -manisidine (Compound 2)can be prepared from m-anisidine and 4-amino-3-propoxy- N-propyl N (fimethylsulfonamidoethyl) -aniline (Compound 4) from 3-propoxyaniline bythis procedure if instead of using ethyl iodide in the first step of thesyntheses, methyl iodide is used for the first compound and propyliodide is used for the second.

The introduction of more than one ethoxy group in the ortho positionswith respect to the primary amino group as well as the introduction ofan alkyl group in one ortho position and an alkoxy group in the othermust be considered part of the present invention. Instead of ethoxygroups, other alkoxy groups may be used, in-

eluding alkoxy groups with additional substitucuts in the aliphaticradical, such as OI-I, C1, OR, etc.

Where we refer to lower alky we mean a methyl, ethyl or propyl group,and where we refer to lower alkoxy we mean a methoxy, ethoxy or propoxygroup.

When used for the formation of colored photo,- graphic images, thedevelopers of our invention may be used in conjunction with any wellknown coupler compounds such as those described in Fischer U. S. Patent1,102,028, June 30, 1914; Mannes and Godowsky U. S. Patent 2,108,602,February 15,1938;Mannes, Godowsky and Peterson U. S. Patent 2,115,934,April 26, 1938; and Marines, Godowsky and Peterson U. S. Patent2,126,337, August 9, 1938.

The following example, which are illustrative only, indicate developingsolutions which may be used according to our invention.

Example 1 4-amino-3-ethoxy-N-ethyl-Ne (pmethylsulfonamidoethyl) -anilinegrams 1 Sodium sulfite do, 0.5

Sodium carbonate do 20 Water to cc 1000 Coupler gram 1 Acetone cc 50AddBtoA EzrampleZ For the formation of a fine grain black-andwhiteimage, the following developing solution may be used:

4 amino N ethyl N (p methylsulfonamidoethyD-m-anisidine grams 5 Sodiumsulfite do 30 Sodium carbonate do 30 Water to cc 1000 eral formula:

wherein R. and R represent lower alkyl groups, and X is selected fromthe class consisting of hydrogen, lower alkyl, and lower alkoxy groups.

2. An amino compound of the following general formula:

CH hNHSOzCH;

wherein R and R represent lower alkyl groups.

3. An amino compound of the following general formula:

R! HgN N\ R (CHzhNHSO GH,

wherein R and R represent lower alkyl groups. 4. An amino compound ofthe following formula 5. An amino compound of the following formula:

CH2) ZNHSO CH,

a m nm N lofiomfisoqom 0H,

6. An amino compound of the following general formula:

OCzHu RI 11,: N

R (CHflgNHSOgCHz wherein R and R represent lower alkyl groups.

'7. An amino compound of the following formula:

1. AN AMINO COMPOUND OF THE FOLLOWING GENERAL FORMULA: